Mixed chromium complex monoazo dyestuffs



United States Patent 3,544,546 MIXED CHROMIUM COMPLEX MONOAZO DYESTUFFS Allen Crabtree and Graham Holmes, Manchester, England, assignors to Imperial Chemical Industries Limited, Millbank, London, England, a corporation of Great Britain No Drawing. Filed Jan. 9, 1967, Ser. No. 607,913 Claims priority, applicatioi17great Britain, Jan. 31, 1966,

66 Int. Cl. cosh 45/16; D06p 1/02 U.S. Cl. 260-145 Claims ABSTRACT OF THE DISCLOSURE where one of the benzene nuclei contains a NHR group; R is a cellulose-reactive group, and other substituents of the kind readily available in o-aminophenols can be present in this or the other benzene nucleus, for example, N0 SO H, C1. The preferred reactive group is the 2- chloro-4-amino-s-triazine group. These dyes are black reactive dyes with very high fixation.

RELEVANT PRIOR ART U.S. Pat. No. 2,929,809, U.S. Pat. No. 2,943,084, U.K. Pat. No. 952,461.

DETAILED DESCRIPTION According to the invention there are provided metal complex reactive dyestuffs having one atom of chromium or cobalt complexly bound to two different metallisable monoazo compounds which together contain at least three cellulose-reactive groups attached to benzene or naphthalene nuclei through a linking nitrogen atom, each cellulosereactive group comprising an acyl or heterocyclic radical containing an atom or group capable of entering into reaction with the hydroxyl groups of the cellulose molecule.

As examples of cellulose-reactive groups there may be mentioned, for example, the radicals of cup-unsaturated aliphatic carboxylic acids such as acrylic acid, oc-ChIO- acrylic acid, propiolic acid, maleic acid and monoand di-chloromaleic acids, and more particularly, the radicals of acids which contain a labile halogen atom or a group which readily splits off to form an anion, for example, the radical of a halogenated aliphatic acid such as chloroacetic acid, fl-chloro and fl-bromo-propionic acids and cupdichloropropionic acid or more especially, a heterocyclic radical which contains from 2 to 3 nitrogen atoms in the heterocyclic ring and at least one labile substituent on a carbon atom of the ring. By a labile substituent there is meant an atom or group which is bound to a carbon atom in ortho position to a nitrogen atom of the heterocyclic ring which atom or group is readily replaced by a hydroxyl group under aqueous alkaline conditions, since such atoms 3,544,546 Patented Dec. 1, 1970 or groups are capable of reacting with hydroxyl groups of the cellulose molecule.

As examples of such heterocyclic radicals, there may be mentioned, for example 2,3-dichloro-quinoxaline-5- or 6- sulphonyl, 2,3-dichloro-quinoxaline-5- or 6-carbonyl, 2,4- dichloro-quinazoline-6- or 7-su1phonyl, 2,4,6-trichloroquinaZoline-7- or 8-sulphonyl, 2,4,7- or 2,4,8-trichloroquinazoline-6-sulphonyl, 2,4-dichloro-quinazoline-6 carbonyl, l,4-dichloro-phthalaZine-6 carbonyl, and, more particularly s-triazine-Z-yl and pyrimidin-2-yl or 4-yl radicals which contain on at least one of the remaining 2,4 or 6 positions, a bromine or, preferably, a chlorine atom, a sulphonic acid group, a thiocyano group, an aryloxy or arylthio group containing an electronegative substituent such as sulphophenoxy, sulphophenylthio, nitrosulphophenoxy, disulphophenoxy and sulphonaphthoxy; or a group of the formula:

wherein Y represents the group of atoms necessary to form a 5- or 6-membered heterocyclic ring which may carry substituents or form part of a fused ring system; or a quaternary ammonium or pyridinium group; or a group of the formula:

wherein R and R each represent the same or different alkyl, cycloalkyl, aryl or aralkyl groups, or R and R together form, together with the nitrogen atom, a 5- or 6- membered heterocyclic ring; or a group of the formula:

wherein R and R may be the same or different and each represents a hydrogen atom or an alkyl, aryl or aralkyl group.

In the cases where the reactive group is a triazine ring carrying only one such labile substitutent, the said ring may have a non-labile substituent on the remaining carbon atom.

By a non-labile substituent there is meant a group which is bound by a covalent bond to the carbon atom of the triazine nucleus, which covalent bond is not ruptured under the conditions used for application of the reactive dye. An example of such substituents, there may be mentioned, for example, primary amino and hydroxyl groups, also monoor di-substituted amino groups etherified hydroxyl and etherified mercapto groups; in the case of substituted amino groups, this class includes, for example, monoand di-alkylamino groups in which the alkyl groups preferably contain at most 4 carbon atoms, and which may also contain such substituents as chlorine atoms or hydroxyl, alkoxy or sulphate groups; and phenylamino and naphthylamino groups preferably containing sulphonic acid substituents; in the case of etherified hydroxyl and mercapto groups, this class includes, for example alkoxy and alkylthio groups preferably those of low molecular weight, i.e. having up to about 4 carbon atoms and phenoxy, phenylthio, naphthoxy or naphthylthio groups; as particular examples of all these classes there may be mentioned, for example, methylamino, ethylamino, dimethylamino, B hydroxyethylamino, di (fi-hydroxyethyDamino, B chloroethylamino, cyclohexylamino, anilino, sulphophenylarnino, disulphophenylamino, N methylsulpho phenylamino, N 3-hydroxyethyl-sulphophenylamino, carboxyphenylamino and sulphocarboxyphenylamino, methoxy, ethoxy and butoxy, phenoxy, methylphenoxy,

chlorophenoxy and phenylthio groups. In the case of pyrimidinyl radicals, chlorine atoms or cyano, nitro, carboxy or carbalkoxy groups in the -position of a pyrimidine nucleus come into the category of non-labile substituents.

It is preferred that each reactive group should be a s-triazinyl radical containing at least one chlorine atom,

above all, the 4-chloro-6-amino-s-triazin-2-yl radical,

or o,o'-dihydroxyphenylazonaphthalene compounds, but

other metallisable monoazo compounds can be present, for example o,o'-di11ydroxyazobenzene compounds, 0- hydroxy-o'-carboxyazobenzene compounds, o-hydroxy phenylazopyrazolone compounds, azo-pyrazolone compounds.

The new dyestuffs contain at least 3 sulphonic acid groups, which may be distributed in any desired manner in the molecule. It is preferred that the dyestuffs should have from 4 to 6 inclusive, sulphonic acid groups, depending on the molecular weight of the dyestulf.

o-hydroxynaphthyl- According to a further feature of the invention, there is provided a process for the manufacture of the new metal-complex reactive dyestuffs which comprises reacting a metal-complex compound having one atom of chromium or cobalt complexly bound to two different metallisable monoazo compounds, which together contain three acrylatable amino groups on benzene or naphthalene nuclei, with the halide or anhydride of an acid carrying a substituent capable of. entering into reaction with the hydroxyl groups of the cellulose molecule, the reactants together containing at least 3 sulphonic acid groups.

The treatment of the metal complex compound with r the acid halide or anhydride can conveniently be carried out by stirring an aqueous solution of the complex with an aqueous suspension or solution of the acid halide or anhydride and is preferably carried out in the presence of an acid-binding agent; the temperature of the reaction can be varied from 0 to 100 C. and will depend on the ease with which water will react with the acid halide or anhydride group or the group capable of reacting with the fibre.

As examples of anhydrides or acid halides which may be used, there may be mentioned, for example, the anhydrides or acid halides of curl-unsaturated aliphatic acids such as chloromaleic anhydride, propiolyl chloride and acrylyl chloride, the acid chlorides of halogenated aliphatic acids such as chloroacetyl chloride, sulpho-chloroacetyl chloride, fl-bromo and fl-chloropropionyl chloride and u:B-dichloropropionylchloride, and preferably, heterocyclic compounds which contain at least 2 nitrogen atoms in the heterocyclic ring and which contain 2 or more halogen, especially chlorine, atoms in the ortho positions to the nitrogen atoms, such as 2,3-dichloroquinoxaline-S- and 6-carboxylic acid chlorides,

2,3-dichloro-quinoxaline-5- and 6-su1phonyl chlorides,

2,4dichloro-quinazoline-6- and 7-sulphonyl chlorides,

2,4,6-trichloro-quinazoline-7- and 8-sulphonyl chlorides, 2,4,7- and 2,4,8-trichloro-quinaZoline-6-sulphonyl chlorides,

2,4-dichloro-quinazoline-fi-carboxylic acid chloride,

4 2,4-dichloro-S-nitro-6-methylpyrimidine, 2,4-dichloro-S-nitropyrimidine, 2,4,6-trichloro-5-cyanopyrimidine, 5-carboxy-2,4-dichloropyrimidine,

S-carboethoxy-2,4-dichloropyrimidine, cyanuric bromide and, preferably cyanuric chloride and the primary condensation products of cyanuric'bromide or cyanuric chloride with ammonia, an alkali'metal sulphite or thiocyanate or an organic mercaptan, hydroxy compound or an organic primary or secondary amine, for example methanol, ethanol, iso-propanol, phenol, 0-, mand pchlorophenols, o-, mand p-cresols, 0-, mand p-sulphophenols, thiophenol, thioglycollic acid, dirnethyldithio carbamic acid, mercaptobenzthiazole, thioacetamide, methyl-, dimethyl-, ethyl-, diethyl, p-propyl, iso-propyl-, butyl-, hexyl or cyolo hexylamine, toluidine, piperidine, morpholine, methoxyethylamine, ethanolamine, aminoacetic acid, aniline-2:5-, 2:4, and 3:5-disulphonic acids, orthanilic, metanilic and sulphanilic acids, 2,3 and 4- aminobenzoic acids, 4- and 5 sulpho-2-aminobenzoic acids, 5-amino-2-hydroxybenzoic acid, Z-aminoethanesulphonic acid, aminonaphthalene rhonoand disulphonic acids and N-methylaminoethane sulphonic acid; also, the secondary condensation products of cyanuric chloride with alkali metal sulphites, alkali metal thiocyanates, phenols and thiophenols containing an electronegative substituent, and compounds of the formulae wherein Y R R R and R Have the meanings stated above. i--**ifl The metal-complex compounds used in the above process can be obtained by reacting together, by methods known per se, one equivalent each of a chromium or cobalt salt and two different metallisable monoazo compounds which together contain 3 acylatable amino groups attached to benzene or naphthalenenuclei. Whilst it is possible to use the mixtures of compounds obtained by a simultaneous reaction of all three reactants, it is preferred, in general, to use a substantially homogeneous metalcomplex compound, obtainable, for example, by first forming a 1: l-chromium or cobalt complex of one metallisable monoazo compound and reacting this complex with the other metallisable monoazo compound. It is preferred that the acylatable amino groups should be distributed so that two are in one monoazo compound and one in the other. The metallisable monoazo compounds can be obtained in the usual manner by coupling together diazo and coupling components having structures leading to the formation of a metallisable monoazo dyestuff, either already containing the desired acylatable amino groups, or containing groups such as acetylamino or nitro which can be converted to amino by reduction or hydrolysis.

Thus one amino group can be introduced into the monoazo compound by using, as diazo component, an o-aminophenol or an anthranilic acid which contains a nitro or acetylamino group, followed, as necessary, by reduction or hydrolysis, or by using a coupling component which couples ortho to a hydroxyl group and which contains an acylatable amino group, either in the same aromatic moiety as the hydroxyl group, as in an aminonaphthol, or in a pendant nucleus, for example in an aminoanilino naphthol or a 1-(aminophenyl)pyrazol-S-one coupling component.

The metal-complex reactive dyestutf in which each cellulose-reactive group is a 4-chloro-6-aminoor substituted amino-s-triazin-Z-yl group can also be obtained by a modification of the above process wherein the metalcomplex compound is reacted with cyanuric chloride and the resultant tris-(dichloro-s-triazine) compound is re- The solution is cooled to 15 C. and added slowly to acted with ammonia or a primary or secondary amine. a stirred suspension of 15 partsof cyanuric chloride in a This modified process can also conveniently be carried mixture of 90 parts of water and 75 parts of acetone mainout in aqueous medium, the first step being preferably tained at C. by cooling, at the same time adding 10% carried out at a temperature of from 0 to C. and the aqueous sodium carbonate solution so that the pH is second at from 30 to 35 C. An acid-binding agent is 0 maintained within the limits of 6.0 and 6.5. The mixture preferably used to neutralise the liberated hydrogen chlois stirred until the cyanuric chloride has appeared to disride, and in the second step this can conveniently be carsolve and HCl is no longer liberated. 25 parts of a 30% ried out by using an excess of the amine or ammonia used aqueous solution of ammonia are then added slowly and as reactant. the solution is heated to 35-40 C. during 1 hour, and According to yet a further feature of the invention there maintained at this temperature for '1 hour. The solution is provided a process for manufacture of the new metalis then filtered and the dyestutf precipitated by addition of complex reactive dyestuffs which comprises reacting a potassium acetate. The dyestulf is filtered off, Washed metallisable monoazo compound with a lzl-chromiumwell with ethanol and dried. or cobalt-complex of a metallisable monoazo compound, When printed on cellulose textiles in the presence of the two metallisable monoazo compounds being different alkali there are obtained neutral black shades of high fixaand so chosen that together they contain 3 cellulose-retion with good fastnessto light and to wet treatments. active groups and at least 3 sulphonic acid groups. The following table gives further examples of the in- This process can conveniently be carried out by stirvention which may be obtained by reacting the 1:1- ring a mixture of the two reactants in an aqueous medichromium complex of the monoazo compound named um at atemperature of from 50 to 60 C. in column II with the monoazo compound named in col- The new metal-complex dyestuffs can be isolated from umn III, reacting the product with the equivalent amount the media in which they have been formed by the normal of cyanuric chloride and reacting the dichlorotriazine so techniques for isolating water-soluble reactive dyes. In formed with the amine listed in column IV. The shades some cases they can be obtained by spray drying the whole obtained when the dyestuffs are printed on cellulose reaction mixture but in general it is preferable to preciptextiles are given in column V.

I 1:1-Chrom1'um complex Monoazo compound Amine Shade 2 Lamina-742-hydroxy-4-sulpho-6-nitronaph- 6-arnino-2-(2-hydroxy-4-sulpho-6-aminonaph- Ammonia. Black.

thylazo)-8-naphthol-3:fi-disulphonie acid. thy]azo-l-naphthol-3-sulphonic acid. 3 6-amino2-(2-hydroxy-4-sulpho-6nitronaph- 1-amino7-(2-carboxy-4-aminophenylazo)-8- do Do.

thylazo)-1-napththol-3-sulphonic acid. naohthol-3z6-disulphonic acid. 4 1-amino-7-(2-hydroxy-5-nitrophenylazo)-8- do do D0.

naohthol-3:6-disulphonic acid. 5 -d0 1-amino-7-(2-hydroxy-3-arn1no-5-sulpho- .do Blue-blacknaphthol-3z6-disu1phonie acid.

itate in the form of an alkali-metal salt, for example, by Example 6 the addition of soffipm chloride and to i ofi.and dry A mixture of 7.35 parts of the 1:1-chromium comthe resultant precipitate. In s0me cases 1t 1s desrrableto plex of Laminofi hydroxy sunitrophenylazo) 8 add Stablhsmg. agents before drymg for exarPPle naphthol-3:6-disulphonic acid and 6.54 parts of l-aminotures of alkah-metal acid phosphates or tertiary alkyl- 40 7 (z, hydroxy 3, amino s, sulphophenylazo) 8 naphthO1 arinne sulpholiatesgs descnbed and claimed m Umted 3:6-disulphonic acid in 250 parts of water at pH 7-8 is Kmgdom speclficatlons 838337 and stirred and boiled under a reflux condenser for 2 hours.

The.new metal'wmplex azo dyestuffs are valuable P The solution is cooled to 15 C. and added slowly to a cellulqsfi textile mammal for example textlle stirred suspension of 7.5 parts of 2:4-dichloro-6-methoxymaterlffls compnsmfg natural. or regenerated cotton For s-triazine in a mixture of 100 parts of water and parts colouring Such textlle materials t new metal complex of acetone maintained at 0-5 C. by external cooling, and am dyestuffs are Preferably apphed either by a dyemg maintaining the pH of the mixture at 6-7 by addition of or printing process, to the cellulose textile materials in 10% sodium carbonate Solution as required. when the conjunction with a treatment With an acid-binding agent, addition is complete the temperature of the mixture is for example sodium hydroxide, sodium carbonate or sodi- 50 raised to 300 C. during 1 hour, and maintained at this um bicarbonate which may be applied to the cellulose textemperature for 1 hour maintaining the PH at tile material before, during or after the application of the throughout by addition of 10% sodium Carbonate as dyestuffs. Alternatively when the colouration process inquireli The Solution is then filtered and the dyestuff Volves the use of heatlng Step a substance i be used precipitated by addition of potassium acetate. The dyel mehloreaeetater whfch 1S Changed stuff is filtered 01f, washed well with ethanol and dried. mto an aeld'bmdmg agent dfnmg the heanng Step When When printed on cellulose textiles in the presence of so applied to cellulose textlle matenals the new metal alkali there are obtained blue/black shades of high fixeomPleX aZO dyestuffs react Wlth the cellulose and can be ation with good fastness to light and to wet treatments. built up to give strong shades, having very good fastness If in place of the lzbchromium complex above there light and to Wet treatments espeelany to Severe Wash 1s used the equivalent amount of the corresponding 1:1- cobalt complex there is obtained a dyestuff which gives The mvemlon 1s lllus-treted but not hmlted by the reddish black shades when printed on cellulose textiles following examples whleh Parts and Percentages are of high fixation and with good fastness to wet treatments by Welght: and to light.

Example 1 Example 7 A mixture of 17.9 parts of the lzl-chromium complex A mixture of 10.0 parts of the lzl-chromium complex of the monoazo compound obtained by the alkaline couof 1-(2'-chloro 4' anilino-s-triazinyl 6'-ylamino)-7- pling of 6-nitro-1-diazo-2-oxynaphthalene-4-sulphonic (2-hydroxy-5'-nitrophenylazo) 8 naphthol-3:6-disulacid With 1hydroxy-8-aminonaphthalene-3:6-disulphonic phonic acid and 13.8 parts of 1-[2'-chloro-4'-(3"-sulphoacid, and 10.4 parts of the monoazo compound obtained anilino)-striazin 6' ylamino] 7-[2'-hydroxy-3-{2- by the alkaline coupling of S-acetylaminomthranilic acid chloro 4" (3"-sulphoanilino)-s-triazin-6"-ylamino}-5'- with Z-amino8-naphthol-6-sulphonic acid followed by hysulphophenylazo]-8-naphthol-3:6-disulphonic acid in 250 drolysis of the acetylamino group, in 300 parts of water parts of water is stirred at pH 6.5 and 70 C. for 3 /2 at pH 8.5 is stirred and boiled under a reflux condenser hours when reaction is usually complete. The solution is for one hour. cooled to 20 C., and the dyestutf precipitated by addi- 8 tion of potassium chloride. The dyestutf is filtered off 3. Metal complex reactive dyes as claimed in claim 1 and dried. wherein the metallisable monoazo compounds are each When printed on cellulose textiles in the presence of represented by the formula alkali there are obtained black shades of high fixation OH OH Nmmy with good fastness to light and to wet treatments. I l

The following table gives further examples of chromium 5 complexes of the invention which may be obtained by the methods described in Examples 1, 6 and 7. Columns SO3H II and 111 name metallisable monoazo compounds bound in the complex and Column lvnames the reactive groups, wherein the benzene nucleus in one of said compounds three of which are attached to the complex through the carries at least a NHY group.

amino groups. 4. A metal complex reactive dye as claimed in claim 1 Ex. Metallisable monoazo compounds Relative Group Shade 3 1-amino-7- -hyd roxy-5 -nitrpphenylazo)-8- 1-amino-7-(2 -hydroxy-3-amino-5'- sulpho- 2-chloro-4-(3 -sulphoanilino)-s- Blue-black.

naphth0l-3:6-d1sulphon1c acid. phenylazo)8-uaphtl1ol-3:G-disulphonic acid. triazin-fi-yl. 9 d0 -d 4 2:4:fitrichloropyrimid-fi-yl D0. 2:4-dicl11or0pyrimid-6 D0. ydroxyB mo-5-sulpho- 2chlo1'o4-amino-striazin-6-y Black. phenylazo)-1-naphthol-3-su1phonic acid. fi-amino-2-(2-hydr0Xy-2-arnino-5-su1phodo D0.

phenylazo)1-naphthol-3:5-disulphonic acid. 13 .-d0 do 2-chloro-4-B-hydroxyethylamino D0.

s-triazin-fi-yl. Do- 2: 4: 5-trichloropyrimid-6-yl D o. 2-chloro-4-(4-fisulphatoethyl- Do.

sulphonylanilino)s-triazin-G- 16 fin 2:4-dichlorophyimid-6-yl D0. 17 do. 2 4-dich1oro-5cyanopyrimid-6-yl D0. 18 do. 1-(phenyl-4-carbonyl) 4 5-dic h- Do.

1or6-pyridazone. 19.. do.. 2:4idlchlorquinazoline-7-carb0n- D0- y 20 -.do .do 2z3-dichlorquinoxaline-ecarbon-yl. D0. 21 methyl-2-(5-aminophenylazo)phenol 8a1nluo-2-(2-hydroxy-3amlno-5-sulpho- 2-chloro-4-(3:5'-disulphoanilino) Do.

phenylazo)-1-naphthol-3zfi-disulphonie acid. s-triazin-dyl. Dlull green- 15 grey. 22 do .do 2-chloro-4-(3-sulphoanilino)-s- Do.

triazin-fi-yl. 23.- 1-ammo-6- '-hydroxy-3{-nitro-SQsulphophenyl- 1-amino-7- '-hydroxy-3-amino-5-su1pho- 2-choro4-amino-s-triazinfi-y] Do.

lazo)-S-naphthol-3:6;d1sulphon1c acid. phenylazo)-8-naphthol-3:G-disulphonic acid. 24 d0 .do 2-chloro 4(4B-sulphatoethyl- D0.

sulphonylanilino)s-triazin-fi-yl. 25 ..d0 -do 2:-dichloro-fi-cyanopyrimidin- D0.

-.y 26.-." 1-amino-7(2'-hydroxy-B(-nitro-Ssulphophenyl- 1-amino-7-(2-hydroxy-3-amino-5-sulpho- 2:3-dichlorqlinoxaline-B-carb011- Black.

azo)-8-naphthol-3:6dlsulphonie acid. phenylazo)-8-naphthol-3:6-disulphonic acid. yl. 27 do dn 2:3idich1orquinoxaline-5-carbon- Do.

y v 28 .do do 2z4-dichlorquinazoline-6-carbon- Do.

29 do do 2:4-dichlorquinazoline-7-earbon- Do.

30 -410 1- -methyl-3-amino-5-snlphophenyl)3-car- 2-chloro-4-amino-s-triazin-fi-yl Brown.

boxy-4-(2-hydroxy-3-arnino-5-sulph0phc11- ylazo)-5-pyrazolone. 31 dO .do 2-cl1loro-4- -sulphoanilino)-s- Do.

triazin-fi-yl. 32 do do 2-chloro-4-(3- 3-sulphatoethyl- Do.

sulphonylanilino)s-triazin-B- 33 -.d0 d0 2:4-dichloro-5-cyanopy1'imid-6-y1 Do. 0-. 2:4:5-t1ichloropyrimid-6-yl Do. 35 .-d0 do 2:3-dichlorquinoxaline-5-carbon- Do.

36 .do do 2-ehlor-4-B- ydroxyethylamino-s- Do.

triazin-dyl.

We claim: being the complex of chromium with 1 mole of the azo 1. A mixed 1:2 complex of chromium with two difcompound of formula ferent metallisable monoazo compounds of which one is 01 selected from the class consisting of o,o'-dihydroxyazoh 1 d'h d h 1 h nap tha ene, 0,0 1 y roxyp eny azonapht alene and o-(o'-carboxyphenylazo) hydroxynaphthalene compounds f and the other is selected from the class consisting of o,o'- OH OH NH-o CNH2 dihydroxyazonaphthalene, o,o'-dihydroxyphenylazonaph- I I I thalene and o-hydroxyphenylazopyrazolone in which the N=N pyrazolone nucleus carries a benzene ring in the l-position, further substituents on the benzene or naphthalene H038 SOaH nuclei in said compounds being selected from the class I consisting of CH N0 SO H and NHY, Y representing N02 a cellulose-reactive heterocyclic radical selected from the and 1 mole of the azo compound of formula class consisting of amino-chloro-s-triazine, methoxy-chlo- O1 ro-s-triazine, p-hydroxyethylamino-chloros-triazine, di- 6 chloropyrimidyl, trichloropyrimidyl, and cyano-dichloropyrimidyl and the total number of 80 1-1 groups in the complex being from 4 to 6 inclusive, and the total num- 7 0H 0H NH-C O-NHZ ber of cellulose-reactive heterocyclic radicals being 3 with 0 l l a maximum of one of said radicals being substituted on NH2-C O-NH- N=N- any one benzene or naphthalene nucleus in the molecule. 'l l 2. Metal complex reactive dyes as claimed in claim 1 HOaS- so tr wherein the metallisable monoazo compounds are both I I o,o'-dihydroxyphenylazo. naphthalene compounds. 01 s 0 H 5. A metal complex reactive dye as claimed in claim 1 being the complex of chromium with 1 mole of the azo compound of formula l0 and 1 mole of the azo compound of formula 011 N I 0H I OH; NH-c C-NH2 C-NH -N=NO=C I I I ll N N N\ C \0/ c 0=c l I I $0311 01 01 503E COzH References Cited FOREIGN PATENTS 1,353,102 1/1964 France.

15 CHARLES B. PARKER, Primary Examiner D. M. PAPUGA, Assistant Examiner US. Cl. X.R. 

